Printed electronics

ABSTRACT

Printed electronic device comprising a substrate onto at least one surface of which has been applied a layer of an electrically conductive ink comprising functionalized graphene sheets and at least one binder. A method of preparing printed electronic devices is further disclosed.

STATEMENT REGARDING RELATED APPLICATIONS

The present application is a divisional of U.S. Ser. No. 12/866,079,filed Nov. 3, 2010, which was a 371 national stage application of PCTapplication PCT/US09/30570, filed Jan. 9, 2009, which claimed priorityto U.S. Provisional application Ser. No. 61/026,273, filed Feb. 5, 2008,the entire contents of each of which are hereby incorporated byreference. The present application claims priority to each of the abovelisted applications.

This invention was made with Government support under Grant No.CMS-0609049, awarded by the National Science Foundation, and under GrantNo. NCC1-02037, awarded by NASA. The government has certain rights inthe invention

FIELD OF THE INVENTION

The present invention relates to printed electronic devices and methodsfor their manufacture.

BACKGROUND

Printed electronics are increasingly finding uses in a great variety ofapplications, including portable electronics, signage, lighting, productidentification, packaging flexible electronic devices (such as thosethat can be rolled or bent), photovoltaic devices, medical anddiagnostic devices, antennas (including RFID antennas), displays,sensors, thin-film batteries, electrodes and myriad others. Printedelectronics have a variety of advantages over electronics made usingother methods, including subtractive methods. Printing can be fasterthan normal subtractive methods (such as etching) and can generate lesswaste and involve the use of fewer hazardous chemicals than in suchmethods. The resulting electronics can be more facilely used in flexibledevices, such as displays, that are designed to be rolled, twisted,bent, or subjected to other distortions during use.

Printed electronics are typically made by printing the electroniccircuit or other component or device on a substrate using anelectrically conductive metal-based ink. The inks typically containsilver particles, and occasionally copper particles, other metallicparticles, and/or conductive polymers. However, conductive polymersalone are generally not sufficiently electrically conductive.Furthermore, the resulting printed metallic circuits are usuallyinsufficiently electrically conductive to be effective in mostapplications, including in devices in which the circuits are regularlystressed by bending and/or stretching during use. The printed substratesmust therefore often be heated at elevated temperatures to sinter theconductive metal particles in order to achieve the desired levels ofelectrical conductivity. The temperatures used in sintering processesfrequently limit the substrates that can be selected for the preparationof the electronics. For example, while it would be desirable to useinexpensive materials such as paper, polyolefins (e.g., polypropylene),and the like as substrates for printed electronics in many applications,the sintering temperatures often required are too high to be used withpaper.

Furthermore, silver is costly and other, non-precious, metals can formoxides upon exposure to the environment that can render the materialinsufficiently conductive for the application. Additionally, the use ofmetal-based inks can add weight to the resulting device, and theaforementioned sintering process can add one or more additional steps,time, and complexity to the fabrication process. It would thus bedesirable to obtain printed electronic devices using inks that do notcontain costly precious metals, that are lighter weight, and that do notrequire sintering to become sufficiently electrically conductive, andthat could therefore be used on a wider variety of substrate materials,including paper and polyolefins such as polyethylene.

U.S. Pat. No. 7,097,788 discloses a method of increasing theconductivity of an ink comprising orienting particles in the ink. U.S.Pat. No. 7,163,734 discloses an element and a method for patterning anorganic polymer electroconductive layer that is suitable as anelectronic circuitry element in an electric or semiconductor device. US2006/0124922 discloses an electrically conductive ink used to formelectrodes for an organic semiconductor transistor. WO 2004/006635discloses a method of printing using an electrically conductive ink. WO2006/108165 discloses a conductive ink containing fine metallicparticles, a polymer base, a solvent, and a nanotubes containingconductive filler. WO 2006/137666 discloses an antenna having an antennaradiator formed by printing electrically conductive ink on a substrate.WO 2007/053621 discloses a method of electrohydrodynamic printing andmanufacturing.

SUMMARY OF THE INVENTION

Disclosed and claimed herein is a printed electronic device, comprisinga substrate comprising at least one surface, wherein a layer of anelectrically conductive ink has been applied to a portion of thesurface, and wherein the ink comprises functionalized graphene sheetsand at least one binder. Further disclosed and claimed herein is amethod for forming the printed electronic device.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an optical microscope image of electrically conductive linesprinted from an ink comprising functionalized graphene sheets embeddedinto poly(ethylene oxide).

DESCRIPTION

As used herein, the term “electrically conductive ink” encompassesmaterials comprising electrically conductive materials suspended and/ordissolved in a liquid, as well as pastes and materials in substantiallysolid form containing little or no liquids. Electrically conductive inksmay be free-flowing, viscous, solid, powdery, and the like. The term“ink” is used to refer to an ink in a form that is suitable forapplication to a substrate, as well as the material after it is appliedto a substrate both before and after any post-application treatments(such as evaporation, cross-linking, curing etc.).

The printed electronic devices (also referred to herein as “printedelectronics) of the present invention may be in the form of completedevices, parts or sub elements of devices, electronic components, andthe like. They comprise a substrate onto at least one surface of whichhas been applied a layer of an electrically conductive ink comprisinghigh surface area functionalized graphene sheets and at least onebinder.

The printed electronics are prepared by applying the ink to a substratein a pattern comprising an electrically conductive pathway designed toachieve the desired electronic device. The pathway may be solid, mostlysolid, in a liquid or gel form, and the like. The ink may furtheroptionally comprise a carrier other than a binder. When the ink has beenapplied to the substrate, all or part of the carrier may be removed toform the electrically conductive pathway. The binder may be cured orcross-linked after the ink has been applied to the substrate.

The printed electronic device formed from the application of the ink tothe substrate may be optionally sintered or otherwise cured, which canresult in the formation of direct bonds between the conducting particlesand thus increase the number of conduction paths. In one embodiment ofthe invention, all or a portion of the device formed from the ink is notsintered and/or not otherwise cured.

To prepare the printed electronic device, the ink may be applied to thesubstrate using any suitable method, including, but not limited to, bysyringe, spray coating, electrospray deposition, ink-jet printing, spincoating, thermal transfer (including laser transfer) methods, screenprinting, rotary screen printing, gravure printing, capillary printing,offset printing, electrohydrodynamic (EHD) printing (a method of whichis described in WO 2007/053621, which is hereby incorporated herein byreference), flexographic printing, pad printing, stamping, xerography,microcontact printing, dip pen nanolithography, laser printing, via penor similar means, and the like.

The substrate may be any suitable material, including, for example,polymers, including thermoplastic and thermoset polymers; pulp productssuch as paper and cardboard (including coated and uncoated materials);synthetic papers; fabrics (including cloths) and textiles; metals;woods; glass and other minerals; silicon and other semiconductors;ceramics; laminates made from a variety of materials; and the like.

Examples of polymers include polyolefins (such as polyethylene,polypropylene, and the like); polyimides; polyesters (such aspoly(ethylene terephthalate), poly(ethylene naphthalate), liquidcrystalline polyesters, and the like); polyamides (includingpolyterephthalamides); aramids (such as Kevlar® and Nomex®);fluoropolymers (such as fluorinated ethylene propylene (FEP),polytetrafluoroethylene (PTFE), poly(vinyl fluoride), poly(vinylidenefluoride), and the like); polyetherimides; poly(vinyl chloride);poly(vinylidene chloride); polyurethanes; cellulosic polymers; SAN; ABS;polycarbonates; polyacrylates; thermoset epoxies and polyurethanes; andelastomers (including thermoplastics and thermosets, and includingrubbers (such as natural rubber) and silicones).

The high surface area functionalized graphene sheets, which are alsoreferred to herein as “FGS”, are graphite sheets having a surface areaof from about 300 to about 2630 m²/g. In some embodiments of the presentinvention, the FGS primarily, almost completely, or completely comprisefully exfoliated single sheets of graphite (often referred to as“graphene), while in other embodiments, they may comprise partiallyexfoliated graphite sheets, in which two or more sheets of graphite havenot been exfoliated from each other. The FGS may comprise mixtures offully and partially exfoliated graphite sheets.

One method of obtaining graphene sheets is from graphite and/or graphiteoxide (also known as graphitic acid or graphene oxide). Graphite may betreated with oxidizing and intercalating agents and exfoliated. Graphitemay also be treated with intercalating agents and electrochemicallyoxidized and exfoliated. Graphene sheets may be formed by ultrasonicallyexfoliating suspensions of graphite and/or graphite oxide in a liquid.Exfoliated graphite oxide dispersions or suspensions can be subsequentlyreduced to graphene sheets. Graphene sheets may also be formed bymechanical treatment (such as grinding or milling) to exfoliate graphiteor graphite oxide (which would subsequently be reduced to graphenesheets). Reduction of graphite oxide to graphene may be by means ofchemical reduction using hydrogen gas or other reducing agents. Examplesof useful chemical reducing agents include, but are not limited to,hydrazines (such as hydrazine, N,N-dimethylhydrazine, etc.), sodiumborohydride, hydroquinone, and the like. For example, a dispersion ofexfoliated graphite oxide in a carrier (such as water, organic solvents,or a mixture of solvents) can be made using any suitable method (such asultrasonication and/or mechanical grinding or milling) and reduced tographene sheets.

In a preferred method, graphite is oxidized to graphite oxide, which isthen thermally exfoliated to form high surface area FGS that are in theform of thermally exfoliated graphite oxide, as described in US2007/0092432, the disclosure of which is hereby incorporated herein byreference. The thusly formed thermally exfoliated graphite oxide maydisplay little or no signature corresponding to graphite or graphiteoxide in its X-ray or electron diffraction patterns.

Graphite oxide may be produced by any method known in the art, such asby a process that involves oxidation of graphite using one or morechemical oxidizing agents and, optionally, intercalating agents such assulfuric acid. Examples of oxidizing agents include nitric acid, sodiumand potassium nitrates, perchlorates, hydrogen peroxide, sodium andpotassium permanganates, phosphorus pentoxide, bisulfites, and the like.Preferred oxidants include KClO₄; HNO₃ and KClO₃; KMnO₄ and/or NaMnO₄;KMnO₄ and NaNO₃; K₂S₂O₈ and P₂O₅ and KMnO₄; KMnO₄ and HNO₃; and HNO₃. Apreferred intercalation agent includes sulfuric acid. Graphite may alsobe treated with intercalating agents and electrochemically oxidized.

Exfoliation, including the exfoliation of graphite oxide is preferablycarried out at temperatures of at least 220° C. or more, preferably attemperatures of from 220to 3000° C.

The FGS used in the present invention preferably have a surface area offrom about 300 to about 2630 m²/g, or more preferably from about 350 toabout 2400 m²/g, or still more preferably of from about 400 to about2400 m²/g, or yet more preferably of from about 500 to about 2400 m²/g.In another preferred embodiment, the surface area is about 300 to about1100 m²/g. A single graphite sheet has a maximum calculated surface areaof 2630 m²/g. The surface area includes all values and subvaluestherebetween, especially including 400, 500, 600, 700, 800, 900, 100,110, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200,2300, 2400, and 2500 m²/g.

Surface area can be measured using either the nitrogen adsorption/BETmethod or, preferably, a methylene blue (MB) dye method.

The dye method is carried out as follows: A known amount of FGS is addedto a flask. At least 1.5 g of MB are then added to the flask per gram ofFGS. Ethanol is added to the flask and the mixture is ultrasonicated forabout fifteen minutes. The ethanol is then evaporated and a knownquantity of water is added to the flask to re-dissolve the free MB. Theundissolved material is allowed to settle, preferably by centrifugingthe sample. The concentration of MB in solution is determined using aUV-vis spectrophotometer by measuring the absorption at λ_(max)=298 nmrelative to that of standard concentrations.

The difference between the amount of MB that was initially added and theamount present in solution as determined by UV-vis spectrophotometry isassumed to be the amount of MB that has been adsorbed onto the surfaceof the FGS. The surface area of the FGS are then calculated using avalue of 2.54 m² of surface covered per one mg of MB adsorbed.

The FGS preferably have a bulk density of from about 40 to about 0.1kg/m³. The bulk density includes all values and subvalues therebetween,especially including 0.5, 1, 5, 10, 15, 20, 25, 30, 35 kg/m³.

The FGS typically have an overall carbon to oxygen molar ratio (C:Oratio), as determined by elemental analysis of at least about 1:1, ormore preferably, at least about 3:2. Examples of carbon to oxygen ratiosinclude about 3:2 to about 85:15; about 3:2 to about 20:1; about 3:2 toabout 30:1; about 3:2 to about 40:1; about 3:2 to about 60:1; about 3:2to about 80:1; about 3:2 to about 100:1; about 3:2 to about 200:1; about3:2 to about 500:1; about 3:2 to about 1000:1; about 3:2 to greater than1000:1; about 10:1 to about 30:1; about 80:1 to about 100:1; about 20:1to about 100:1; about 20:1 to about 500:1; about 20:1 to about 1000:1.In some embodiments of the invention, the carbon to oxygen ratio is atleast about 10:1, or at least about 20:1, or at least about 35:1, or atleast about 50:1, or at least about 75:1, or at least about 100:1, or atleast about 200:1, or at least about 300:1, or at least about 400:1, orat least 500:1, or at least about 750:1, or at least about 1000:1.

The carbon to oxygen ratio also includes all values and subvaluesbetween these ranges.

The inks used in the present invention may optionally contain additionalelectrically conductive components other than the functionalizedgraphene sheets, such as metals (including metal alloys), conductivemetal oxides, polymers, carbonaceous materials other than the highsurface area functionalized graphene sheets, and metal-coated materials.These components can take a variety of forms, including particles,powders, flakes, foils, needles, etc.

Examples of metals include, but are not limited to silver, copper,aluminum, platinum, palladium, nickel, chromium, gold, bronze, and thelike. Examples of metal oxides include antimony tin oxide and indium tinoxide and materials such as fillers coated with metal oxides. Metal andmetal-oxide coated materials include, but are not limited to metalcoated carbon and graphite fibers, metal coated glass fibers, metalcoated glass beads, metal coated ceramic materials (such as beads), andthe like. These materials can be coated with a variety of metals,including nickel.

Examples of electrically conductive polymers include, but are notlimited to, polyacetylene, polyethylene dioxythiophene, polyaniline,polypyrrole, and the like.

Examples of carbonaceous materials other than the high surface areafunctionalized graphene sheets include, but are not limited to, carbonblack, graphite, carbon nanotubes, vapor-grown carbon nanofibers, carbonfibers, metal coated carbon fibers.

Preferred binders are polymeric binders. Polymeric binders can bethermoplastics or thermosets and may be elastomers. Binders may alsocomprise monomers that can be polymerized before, during, or after theapplication of the ink to the substrate. Polymeric binders may becross-linked or otherwise cured after the ink has been applied to thesubstrate. Examples of preferred polymeric binders include polyetherssuch as poly(ethylene oxide)s (also known as poly(ethylene glycol)s,poly(propylene oxide)s (also known as poly(propylene glycol)s, ethyleneoxide/propylene oxide copolymers, cellulosic resins (such as ethylcellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose,cellulose acetate, cellulose acetate propionates, and cellulose acetatebutyrates), and poly(vinyl butyral), polyvinyl alcohol and itsderivatives, ethylene/vinyl acetate polymers, acrylic polymers andcopolymers, styrene/acrylic copolymers, styrene/maleic anhydridecopolymers, isobutylene/maleic anhydride copolymers, vinylacetate/ethylene copolymers, ethylene/acrylic acid copolymers,polyolefins, polystyrenes, olefin and styrene copolymers, epoxy resins,acrylic latex polymers, polyester acrylate oligomers and polymers,polyester diol diacrylate polymers, UV-curable resins, and polyamide,including polyamide polymers and copolymers (i.e., polyamides having atleast two different repeat units) having melting points between about120 and 255° C. (such as those sold under the trade names Macromelt byHenkel and Versamid by Cognis).

The inks may optionally comprise one or more carriers in which some orall of the components are dissolved, suspended, or otherwise dispersedor carried. Examples of suitable carriers include, but are not limitedto, water, distilled or synthetic isoparaffinic hydrocarbons (suchIsopar® and Norpar® (both manufactured by Exxon) and Dowanol®(manufactured by Dow), citrus terpenes and mixtures containing citrusterpenes (such as Purogen, Electron, and Positron (all manufactured byPurogen)), limonene, aliphatic petroleum distillates, alcohols (such asmethanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol,sec-butanol, tert-butanol, diacetone alcohol, butyl glycol, and thelike), ketones (such as acetone, methyl ethyl ketone, cyclohexanone,i-butyl ketone, 2,6,8,trimethyl-4-nonanone and the like), esters (suchas methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate,n-butyl acetate, i-butyl acetate, carbitol acetate, and the like),glycol ethers (such as propylene glycol monomethyl ether and otherpropylene glycol ethers, ethylene glycol monobutyl ether and otherethylene glycol ethers, ethylene and propylene glycol ether acetates),N-methyl-2-pyrrolidone, and mixtures of two or more of the foregoing andmixtures of one or more of the foregoing with other carriers. Preferredsolvents include low- or non-VOC solvents, non-hazardous air pollutionsolvents, and non-halogenated solvents.

The inks may optionally comprise one or more additional additives, suchas dispersion aids (including surfactants, emulsifiers, and wettingaids), adhesion promoters, thickening agents (including clays),defoamers and antifoamers, biocides, additional fillers, flow enhancers,stabilizers, cross-linking and curing agents, and the like. In oneembodiment of the present invention, the surfactant is at least oneethylene oxide/propylene oxide copolymer.

The inks may also optionally comprise one or more prepolymers,oligomers, photo-initiators, and additional additives to allow forcuring by UV, electron beam, or infra-red radiation.

Examples of dispersing aids include glycol ethers (such as poly(ethyleneoxide), block copolymers derived from ethylene oxide and propylene oxide(such as those sold under the trade name Pluronic® by BASF), acetylenicdiols (such as 2,5,8,11-tetramethyl-6-dodecyn-5,8-diol ethoxylate andothers sold by Air Products under the trade names Surfynol® and Dynol®),salts of carboxylic acids (including alkali metal and ammonium salts),and polysiloxanes.

Examples of grinding aids include stearates (such as Al, Ca, Mg, and Znstearates) and acetylenic diols (such as those sold by Air Productsunder the trade names Surfynol® and Dynol®).

Examples of adhesion promoters include titanium chelates and othertitanium compounds such as titanium phosphate complexes (including butyltitanium phosphate), titanate esters, diisopropoxy titaniumbis(ethyl-3-oxobutanoate, isopropoxy titanium acetylacetonate, andothers sold by Johnson-Matthey Catalysts under the trade name Vertec.

Examples of thickening agents include glycol ethers (such aspoly(ethylene oxide), block copolymers derived from ethylene oxide andpropylene oxide (such as those sold under the trade name Pluronic® byBASF).

The inks are electrically conductive and preferably have a conductivityof at least about 10⁻⁸ S/cm. In one embodiment of the invention, whencomponents of the printed electronic devices made from the inks are usedas semiconductors, they preferably have a conductivity of about 10⁻⁸S/cm to about 10³ S/cm, or more preferably of about 10⁻⁷ S/cm to about10³ S/cm. In another embodiment of the invention, the inks preferablyhave a conductivity of at least about 10² S/cm, or more preferably atleast about 10³ S/cm, or yet more preferably at least about 10⁴ S/cm.The conductivities of the inks are determined after they have beenapplied to the substrate and subjected to any post-applicationtreatments (such drying, curing, cross-linking, etc.).

The FGS are preferably present in the ink in at least about 0.01 weightpercent based on the total weight of the ink. In one embodiment of theinvention, the FGS are preferably present in the ink in at least about0.01 weight percent, or more preferably in at least about 0.05 weightpercent, or yet more preferably in at least about 0.1 weight percent, orstill more preferably in at least about 0.5 weight percent, or even morepreferably in at least about 1 weight percent, where the weightpercentages are based on the total weight of the ink after it has beenapplied to the substrate and subjected to any post-applicationtreatments (such drying, curing, cross-linking, etc.). However, as willbe appreciated by those skilled in the art, the amount of FGS present inthe inks can be selected based on the desired electrical conductivityand the particular binders and other optional components chosen.

The inks preferably contain a sufficient amount of FGS such that theyhave electrical conductivities that are greater than those of thecorresponding materials containing each component of the ink in questionexcept for the FGS.

The inks may be made using any suitable method, including wet or drymethods and batch, semi-continuous, and continuous methods.

For example, components of the inks, such as two or more of thefunctionalized graphene sheets, binders, carriers, and/or othercomponents may be blended by using suitable mixing, dispersing, and/orcompounding techniques and apparatus, including ultrasonic devices,high-shear mixers, two-roll mills, three-roll mills, cryogenic grindingcrushers, extruders, kneaders, double planetary mixers, triple planetarymixers, high pressure homogenizers, ball mills, attrition equipment,sandmills, and horizontal and vertical wet grinding mills, and the like.

The resulting blends may be further processed using wet or dry grindingtechnologies. The technologies can be continuous or discontinuous.Examples include ball mills, attrition equipment, sandmills, andhorizontal and vertical wet grinding mills. Suitable materials for useas grinding media include metals, carbon steel, stainless steel,ceramics, stabilized ceramic media (such as yttrium stabilized zirconiumoxide), PTFE, glass, tungsten carbide, and the like.

After blending and/or grinding steps, additional components may be addedto the inks, including, but not limited to, thickeners, viscositymodifiers, and the like. The inks may also be diluted by the addition ofmore carrier.

After they have been printed on a substrate, the inks may be cured usingany suitable technique, including drying and oven-drying (in air oranother inert or reactive atmosphere), UV curing, IR curing, microwavecuring or drying, and the like.

The printed electronic devices of the present invention may take on avariety of forms. They may contain multiple layers of electroniccomponents (e.g. circuits) and/or substrates. All or part of the printedlayer(s) may be covered or coated with another material such as a covercoat, varnish, cover layer, cover films, dielectric coatings,electrolytes and other electrically conductive materials, and the like.There may also be one or more materials between the substrate andprinted circuits. Layers may include semiconductors, metal foils, anddielectric materials.

The printed electronics may further comprise additional components, suchas processors, memory chips, other microchips, batteries, resistors,diodes, capacitors, transistors, and the like.

The printed electronic devices may take on a wide variety of forms andbe used in a large array of applications. Examples include but are notlimited to: passive and active devices and components; electrical andelectronic circuitry, integrated circuits; flexible printed circuitboards; transistors; field-effect transistors; microelectromechanicalsystems (MEMS) devices; microwave circuits; antennas; indicators;chipless tags (e.g. for theft deterrence from stores, libraries, and thelike); smart cards; sensors; liquid crystalline displays (LCDs);signage; lighting; flat panel displays; flexible displays, includinglight-emitting diode, organic light-emitting diode, and polymerlight-emitting diode displays; backplanes and frontplanes for displays;electroluminescent and OLED lighting; photovoltaic devices—backplanes;product identifying chips and devices; batteries, including thin filmbatteries; electrodes; indicators; printed circuits in portableelectronic devices (for example, cellular telephones, computers,personal digital assistants, global positioning system devices, musicplayers, games, calculators, and the like); electronic connections madethrough hinges or other movable/bendable junctions in electronic devicessuch as cellular telephones, portable computers, folding keyboards, andthe like); wearable electronics; and circuits in vehicles, medicaldevices, diagnostic devices, instruments, and the like.

Preferred electronic devices are radiofrequency identification (RFID)devices and/or components thereof and/or radiofrequency communicationdevice. Examples include, but are not limited to, RFID tags, chips, andantennas. The RFID devices may be ultrahigh frequency RFID devices,which typically operate at frequencies in the range of about 868 toabout 928 MHz. Examples of uses for RFIDs are for tracking shippingcontainers, products in stores, products in transit, and parts used inmanufacturing processes; passports; barcode replacement applications;inventory control applications; pet identification; livestock control;contactless smart cards; automobile key fobs; and the like.

EXAMPLES General details for Examples 1-3 and Comparative Example 1

Graphite oxide is prepared from graphite by treatment with sulfuricacid, nitric acid, and potassium chlorate and then thermally exfoliatedto form FGS according to the methods disclosed in Staudenmaier, L. Ber.Stsch. Chem. Ges. 1898, 31, 1481 and Schniepp, H. C. et al. J. Phys.Chem. B. 2006, 110, 8535-8539 (and its Supporting Information) andMcAllister, M. J. et al. Chem. Materials 2007 194396-4404.

The inks are prepared as follows. A poly(ethylene oxide) (PEO) solutionis prepared by mixing a sufficient amount of PEO with a 1:1volume/volume mixture of ethanol and de-ionized water to produce amixture containing 40 mg of PEO per mL of total solvent. After stirringovernight, a homogeneous PEO stock solution is obtained.

FGS is weighed and a sufficient amount of concentrated aqueous PluronicF127 (an ethylene oxide/propylene oxide copolymer surfactant supplied byBASF) solution (typically 2 mg/mL) is added to the FGS to yield amixture having a 1:1 weight ratio of FGS and Pluronic F127. Sufficientde-ionized water is added to produce a suspension containing 1 mg FGSper 1 ml of water. The resulting suspension is sonicated for 5 minuteswith a duty cycle of 20 percent in an ice bath. 1 mL of the FGSsuspension is then added to 3 mL of the PEO stock solution and themixture is stirred for 3-5 minutes until homogeneous.

Example 1

An ink is prepared as described above using PEO having a molecularweight of 4,000,000. The ink is printed electrohydrodynamically onto aglass substrate using the method disclosed in WO 2007/053621. Theprinting is done at a flow rate of 0.5 mL/hr under a 2200 kV potentialdifference between electrodes that are 7.2 mm apart. The width of thelines is about 43 pm. FIG. 1 is an optical microscope image of a seriesof parallel printed lines.

Copper tapes are attached to the lines perpendicular to the length ofthe lines. A power supply (Tektronix PS 252G Programmable Power Supply,Tektronix Inc., Beaverton, Oreg.) and a multimeter (Fluke 27 Multimeter,Fluke Corp., Everett, Wash.) are attached in serial with the printed viathe copper tapes. A potential difference (5-20 V) is applied and currentis monitored through the multimeter. An electrometer (Keithley 6514,Keithley Instruments Inc., Cleveland, Ohio) with two electrodes is usedto measure the potential difference across two points along thedirection of the current. The potential difference measured on the filmand current is used to find the resistance using Ohm's law, i.e. R=V/I;where R, V, and I are the resistance, voltage, and current,respectively. Resistivity (σ) is found by σ=RA/L, where A and L are thecross section of the film through which current flows and the lengthover which the potential difference is measured. Conductivity (κ) isfound by κ=1/σ. The resulting conductivity is about 0.05 S/m.

Example 2

An ink is prepared as described above using PEO having a molecularweight of 4,000,000. The ink is printed electrohydrodynamically onto aglass substrate using the method disclosed in WO 2007/053621. Theprinting is done at a flow rate of 0.5 mL/hr under a 2200 kV potentialdifference between electrodes that are 7.2 mm apart. The width of thelines is about 130 μm.

The ink is formed into a film as follows: two copper plates (22 mm×22mm) are wrapped with Teflon tape, leaving 1 mm of copper uncovered atthe lower ends. The plates are then firmly attached to the shorter ofthe side walls of a Teflon® cell (23 mm×46 mm inner base area, 32 mmheight) with screws. The mixture is poured into the Teflon® cell andkept at 50° C. on a hot plate until all of the solvent is evaporated toform films that are attached to the copper plates.

Copper tapes are attached parallel to each other on two ends of the filmsuch that they cover the entire width of the film. The electricalconductivity of the film is measured across the copper tapes asdescribed above for Example 1. The measured conductivity is about 12.4S/m.

Comparative Example 1

An ink is prepared as described above substituting carbon black(supplied by Cabot Corp.) for the FGS and using PEO having a molecularweight of 300,000. The ink is printed electrohydrodynamically onto aglass substrate using the method disclosed in WO 2007/053621. Theprinting is done at a flow rate of 0.5 mL/hr under a 2200 kV potentialdifference between electrodes that are 7.2 mm apart. The width of thelines is about 130 μm.

As described above for Example 2, the ink is formed into a film and itselectrical conductivity is measured. The result is about 1.3×10⁻⁸ S/m.

Example 3

An ink is prepared as described above using PEO having a molecularweight of 4,000,000. The ink is printed electrohydrodynamically onto aglass substrate using the method disclosed in WO 2007/053621. Theprinting is done at a flow rate of 0.5 mL/hr under a 2200 kV potentialdifference between electrodes that are 7.2 mm apart. The width of thelines is about 140 μm and the thickness is about 300 nm. The printedline has an electrical conductivity of about 19.6 S/m.

General details for Examples 4-14

Preparation of Test Samples

The inks in the form of liquid dispersions are printed onto a substrateusing a doctor blade and then dried in air in an oven at 125° C. to forma film. Testing is done on the printed films.

Electrical Conductivity

The point-to-point resistivity (in ohms) of the films is measured usinga standard multimeter across contact points consisting of two spots ofsilver paste having a diameter of about 0.3 mm that are applied to thesurface of the film about 1 inch apart. The resistance across thesepoints is also measured using a standard multimeter and the reading isdivided by 10 to calculate the resistivity in ohms/square. Results givenas a single number are an average of several measurements and resultsgiven as a range of figures indicate the high and low readings fromseveral measurements.

Peel Resistance

A fingernail is drawn back and forth across the surface of the film fivetimes. The surface of the film where it was scratched and the tip of thenail are examined and the scratch resistance of the film is assessed asfollows: excellent is no noticeable transfer of the film surface to thenail; very good is minimal transfer and no noticeable indentation on thesurface of the film; good is some indentation of the film surface; fairis removal of a substantial portion of the film; and poor is where thesubstrate is visible. In some cases no cohesive film adhered to thesubstrate is formed.

Scratch Resistance

A fingernail is drawn across the surface of the film. The film and tipof the nail are visually inspected. The scratch resistance is graded asfollows: no transfer of film material to the finger nail=excellent;about 10 percent transfer=very good; about 20 percent transfer=good/verygood; about 30 percent transfer=good; about 40 percenttransfer=fair/good; about 50 percent transfer=fair; about 65 percenttransfer=poor/fair; about 85 percent transfer=poor; and about 100percent transfer (the substrate is fully visible and very little to noprinted material remains)=very poor.

Ink Preparation Methods

-   Ball mill A: An Eiger Mini 250 Type M250-VSE-TEFV horizontal    grinding mill

Ball mill B: A vertical stainless steel vertical grinding mill havingfour stainless steel arms situated 90° away from each other. The mill isdriven by a compressed air motor and has a bottom discharge valve.

High shear mixer: A homogenizer having a roto-stator overhead stirrer.

Ingredients Used in the Formulations:

Electron and Positron are citrus terpene-based solvents supplied byEcolink, Tucker Ga.

Example 4

A 4.9 weight percent aqueous solution of poly(ethylene oxide) (PEO)having an average molecular weight of 600,000 (236.2 g) is combined withFGS having a C:O ratio of approximately 100:1 (2.4 g), ethyleneoxide/propylene oxide copolymer surfactant (Pluronic F127, supplied byBASF) (2.4 g), antifoaming agent (AF 204, supplied by Sigma) (0.3 g),and water (50 g). The mixture is ground in ball mill B at 650 rpm using3/16″ stainless steel balls as a grinding medium for 6 hours. Theresulting dispersion is printed onto thermally stabilized PET, coatedpaper, and uncoated paper and the adhesion properties and electricallyresistivity of the resulting printed films are measured. The results aregiven in Table 1.

Example 5

A 10.8 weight percent aqueous solution of poly(ethylene oxide) (PEO)having an average molecular weight of 600,000 (110.8 g) is combined withFGS having a C:O ratio of approximately 100:1 (2.4 g), surfactant(Surfynol 104H, supplied by Air Products) (2.4 g), antifoaming agent (AF204, supplied by Sigma) (0.2 g), and water (134.2 g). The mixture isground in ball mill B at 693 rpm using 3/16″ stainless steel balls as agrinding medium for six hours. The resulting dispersion is printed ontoto thermally stabilized PET, coated paper, and uncoated paper and theadhesion properties and electrically resistivity of the resultingprinted films are measured. The results are given in Table 1.

TABLE 1 Thermally stabilized PET Coated Paper Uncoated paper Peel Resis-Peel Resis- Peel Resis- resis- tivity resis- tivity resis- tivity tance(Ω/sq.) tance (Ω/sq.) tance (Ω/sq.) Example 4 Good 5-10 Fair/good 7-10Poor 4-5 Example 5 Fair/good 10 Fair/good 8-12 Poor 6-7

Examples 6-12

In the case of Examples 6-10, a 20 weight percent solution of polyamidebinder (Versamid 750, supplied by Cognis) in isopropyl alcohol (200 g)is combined with FGS having a C:O ratio of approximately 100:1 (10 g)and additional isopropyl alcohol (40 g). In the case of Examples 18 and19, a 20 weight percent solution of polyamide binder (Versamid 750,supplied by Cognis) in isopropyl alcohol (70 g) is combined with FGShaving a C:O ratio of approximately 100:1 (6 g) and additional isopropylalcohol (124 g).

In all cases, the resulting suspensions are ground for 1.5 hours at 100°F. in ball mill A at 5000 rpm for 1.5 hours using 0.3 mm 5% yttriumstabilized zirconium oxide as the grinding medium. In the cases ofExamples 7 and 10, BYK-ES80 (an alkylolammonium salt of an unsaturatedacidic carboxylic acid ester supplied by BYK USA, Wallingford, Conn.)(0.2 g) is added to 10 g of the resulting dispersion. In the cases ofExamples 9 and 12, a 10 weight percent solution of polyaniline (PANI)(Panipol F, supplied by Panipol Oy, Porvoo, Finland) in chloroform (2 g)is added to 10 g of the resulting dispersion. After each of theseadditives is added, the resulting mixture is blended for about a minutein the high shear mixer. In each case the resulting dispersion isprinted onto thermally stabilized PET and the adhesion properties andelectrical resistivity of the printed films are measured. The resultsare given in Table 2.

TABLE 2 Peel Scratch Resistivity Additive resistance resistance (Ω/sq.)Example 6 none Excellent Excellent 15 Example 7 BYK Very good Very good12 Example 8 none Excellent Excellent 18-23 Example 9 PANI ExcellentExcellent 15-25 Example 10 BYK Excellent Excellent 15 Example 11 noneExcellent Excellent 20 Example 12 PANI Good Good 17

1. A printed electronic device, comprising a substrate comprising atleast one surface, wherein a layer of an electrically conductive ink hasbeen applied to a portion of the surface, and wherein the ink comprisesfunctionalized graphene sheets and at least one binder.
 2. The device ofclaim 1, wherein the substrate comprises paper and/or cardboard.
 3. Thedevice of claim 1, wherein the substrate comprises at least onepolyolefin.
 4. The device of claim 1, wherein the substrate comprises atleast one polyimide.
 5. The device of claim 1, wherein the ink furthercomprises at least one dispersant.
 6. The device of claim 1, wherein thebinder is a polymeric binder.
 7. The device of claim 6, wherein thebinder is one or more of poly(ethylene oxide), poly(propylene oxide),and ethylene oxide/propylene oxide copolymers.
 8. The device of claim 1,wherein the ink further comprises at least one metal component.
 9. Thedevice of claim 8, wherein the metal is silver and/or copper.
 10. Thedevice of claim 1, wherein the ink further comprises at least oneelectrically conductive polymer.
 11. The device of claim 1, wherein theink further comprises at least one carbonaceous material other than thefunctionalized graphene sheets.
 12. The device of claim 1, wherein thefunctionalized graphene sheets have a surface area of from about 300 toabout 2630 m²/g.
 13. The device of claim 1, wherein the functionalizedgraphene sheets have a surface area of from about 400 to about 2400m²/g.
 14. The device of claim 1, wherein the functionalized graphenesheets have a carbon to oxygen ratio of about 60:40 to 20:1.
 15. Thedevice of claim 1, further comprising one or more components selectedfrom the group consisting of processors, memory chips, batteries,resistors, diodes, capacitors, and transistors.
 16. A method for forminga printed electronic device, comprising the step of applying anelectrically conductive ink to a substrate, wherein the ink comprisesfunctionalized graphene sheets and at least one binder.
 17. The methodof claim 16, wherein the substrate is selected from one or more ofpaper, cardboard, polyolefin, and polyimide.
 18. The method of claim 16,wherein the electrically conductive ink further comprises a carrier. 19.The method of claim 16, wherein the electrically conductive ink furthercomprises a dispersant.
 20. The method of claim 6, wherein thefunctionalized graphene sheets have a surface area of from about 300 toabout 2630 m²/g.